Phosphorylated aza compounds

ABSTRACT

The invention relates to new phosphorylated aza compounds, to processes for their preparation and to their use as pesticides, in particular as soil-acting insecticides and nematicide. 
     The new compounds have the general formula (I) ##STR1## in which R 1  -R 5 , X and Y are defined as in the specification, with the exception of compound O-ethyl S-propyl 3-(6-chloro-3-pyridinylmethyl)-2-nitroimino-imidazolidine-1-thiophosphate.

This application is the 371 of PCT/EP92/01184, filed May, 26, 1992.

The invention relates to new phosphorylated aza compounds, to processesfor their preparation and to their use as pesticides, in particular assoil-acting insecticides and nematicides.

It has been disclosed that certain phosphorylated aza compounds, suchas, for example, O-ethyl S-(1-methylpropyl)(2-oxo-3-thiazolidinyl)phosphonothioate/fosthiazate, can be used asinsecticides, acaricides and nematicides (cf. U.S. Pat. No. 4,590,182).However, the activity of these known compounds is not entirelysatisfactory, in particular at low application rates and concentrationsof active compound.

Furthermore, certain optionally phosphorylated aza compounds, such as,for example,N-nitro-1-(6-chloro-3-pyridinyl-methyl)-4,5-dihydro-1H-imidazol-2-amine(imidaclopyrid), diethyl3-(2-chloro-5-thiazolyl-methyl)-2-nitroimino-imidazolidine-1-phosphonate,dimethyl3-(6-chloro-3-pyridinyl-methyl)-2-nitroimino-imidazolidine-1-phosphonate,O,O-diethyl3-(6-chloro-3-pyridinyl-methyl)-2-nitroimino-imidazolidine-1-thiophosphonate,O-ethyl S-propyl3-(6-chloro-3-pyridinylmethyl)-2-nitroimino-imidazolidine-1-thiophosphonateand dimethyl2-nitroimino-3-(3-pyridinyl-methyl)-imidazolidine-1-phosphonate, havebeen disclosed as potential insecticides (cf. EP-A 192,060 and JP-A63156786/Chem. Abstracts 110:8210d).

However, nothing has been disclosed about the possibility of also beingable to combat at the same time insects and nematodes in the soil, usingthese compounds.

The present invention relates to the phoshorylated aza compounds of thegeneral formula (I) ##STR2## in which R¹ represents a five- orsix-membered heterocyclic group which contains 1, 2, 3 or 4 nitrogenatoms and/or one or two oxygen or sulphur atoms as hetero atom ringmembers, the number of hetero atoms being 1, 2, 3 or 4, and which isoptionally substituted by halogen, cyano, nitro, alkyl, halogenoalkyl,alkenyl, halogenoalkenyl, alkinyl, alkoxy, halogenoalkoxy, alkenyloxy,halogenoalkenyloxy, alkinyloxy, alkylthio, halogenoalkylthio,alkenylthio, halogenoalkenylthio, alkinylthio, alkylsulphinyl,halogenoalkylsulphinyl, alkylsulphonyl, halogenoalkylsulphonyl, amino,alkylamino, dialkylamino, aryl, aryloxy, arylthio, arylamino, aralkyl,formylamino, alkylcarbonylamino, formyl, carbamoyl, alkylcarbonyl and/oralkoxycarbonyl,

R² represents hydrogen or alkyl,

R³ represents hydrogen or alkyl or together with R² representsalkanediyl,

R⁴ represents alkyl,

R⁵ represents alkyl,

X represents oxygen or sulphur and

Y represents nitro or cyano,

with the exception of the compound O-ethyl S -propyl3-(6-chloro-3-pyridinylmethyl)-2-nitroimino-imidazolidine-1-thiophosphonate.

Surprisingly, the compounds of the formula (I) display a considerablymore powerful insecticidal activity, in particular against soil-dwellinginsects, than the known compound O-ethyl S-(1-methylpropyl)(2-oxo-3-thiazolidnyl)-phosphonothioate and, in contrast to activecompounds of the prior art which are related from the point of view oftheir structure, also have a very powerful activity againstsoil-dwelling insects and soil-dwelling nematodes.

Formula (I) provides a general definition of the phosphorylated azacompounds according to the invention. In formula (I),

R¹ preferably represents a five- or six-membered heterocyclic group fromthe series consisting of furyl, thienyl, pyrrolyl, pyrazolyl,imidazolyl, 1,2,3- or 1,2,4-triazolyl, oxazolyl, isoxazolyl, 1,2,4- or1,3,4-oxadiazolyl, thiazolyl, isothiazolyl, 1,2,3-, 1,2,4-, 1,2,5- or1,3,4-thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl and pyrazinyl,each of which is optionally substituted by fluorine,chlorine, bromine,iodine, cyano, nitro, C₁ -C₄ -alkyl (which is optionally substituted byfluorine and/or chlorine), C₂ -C₄ -alkenyl (which is optionallysubstituted by fluorine and/or chlorine), C₂ -C₄ -alkinyl, C₁ -C₄-alkoxy (which is optionally substituted by fluorine and/or chlorine),C₃ -C₄ -alkenyloxy (which is optionally substituted by fluorine and/orchlorine), C₃ -C₄ -alkinyloxy, C₁ -C₄ -alkylthio (which is optionallysubstituted by fluorine and/or chlorine), C₃ -C₄ -alkenylthio (which isoptionally substituted by fluorine and/or chlorine), C₃ -C₄-alkinylthio, C₁ -C₄ -alkylsulphinyl (which is optionally substituted byfluorine and/or chlorine), C₁ -C₄ -alkylsulphonyl (which is optionallysubstituted by fluorine and/or chlorine), amino, C₁ -C₄ -alkylamino,di-(C₁ -C₄ -alkyl)-amino, phenyl, phenoxy, phenylthio, phenylamino,benzyl, formylamino, C₁ -C₄ -alkyl-carbonylamino, formyl, carbamoyl, C₁-C₄ -alkyl-carbonyl and/or C₁ -C₄ -alkoxy-carbonyl,

R² preferably represents hydrogen or C₁ -C₃ -alkyl,

R³ preferably represents hydrogen or C₁ -C₃ -alkyl or together with R²represents C₂ -C₄ -alkanediyl,

R⁴ preferably represents C₁ -C₄ -alkyl,

R⁵ preferably represents C₁ -C₅ -alkyl,

X preferably represents oxygen or sulphur and

Y preferably represents nitro or cyano,

with the exception of the compound O-ethyl S-propyl3-(6-chloro-3-pyridinylmethyl)-2-nitroiminoimidazolidine-1-thiophosphonate.

Particularly preferred compounds of the formula (I) are those in which

R¹ represents a five- or six-membered heterocyclic group from the seriesconsisting of pyrazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl,thiazolyl, isothiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrazinyl andpyrimidinyl, each of which is optionally substituted by fluorine,chlorine, bromine, cyano, nitro, C₁ -C₂ -alkyl (which is optionallysubstituted by fluorine and/or chlorine), C₁ -C₂ -alkoxy (which isoptionally substituted by fluorine and/or chlorine), C₁ -C₂ -alkylthio(which is optionally substituted by fluorine and/or chlorine) or C₁ -C₂-alkylsulphonyl (which is optionally substituted by fluorine and/orchlorine),

R² represents hydrogen or methyl,

R³ represents hydrogen or methyl or together with R² representsdimethylene or trimethylene,

R⁴ represents ethyl, propyl or isopropyl,

R⁵ represents ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl,

X represents oxygen or sulphur and

Y represents nitro or cyano,

with the exception of the compound O-ethyl S-propyl3-(6-chloro-3-pyridinylmethyl)-2-nitroimino-imidazolidine-1-thiophosphonate.

Very particularly preferred new compounds of the formula (I) are thosein which

R¹ represents 6-chloro-3-pyridinyl or 2-chloro-5-thiazolyl,

R² and R³ together represent dimethylene (--CH₂ CH₂ --) or trimethylene(--CH₂ CH₂ CH₂ --)

R⁴ represents ethyl,

R⁵ represents sec-butyl,

X represents oxygen or sulphur and

Y represents nitro.

The compounds of the formula (I) are obtained when

(a) aza compounds of the general formula (II) ##STR3## in which R¹, R²,R³ and Y have the abovementioned meaning, are reactedwith-chloro(di)thiophosphoric acid O,S-diesters of the general formula(III) ##STR4## in which R⁴, R⁵ and X have the abovementioned meaning, ifappropriate in the presence of an acid acceptor and, if appropriate, inthe presence of a diluent, or when

(b) heterocyclylmethyl chlorides of the general formula (IV)

    R.sup.1 --CH.sub.2 --Cl                                    (IV)

in which

R¹ has the abovementioned meaning, are reacted with phosphorylated azacompounds of the general formula (V) ##STR5## in which R², R³, R⁴, R⁵, Xand Y have the abovementioned meaning,

if appropriate in the presence of an acid acceptor and, if appropriate,in the presence of a diluent.

If, for example,1-(2-chloro-5-thiazolyl-methyl)-2-nitro-imino-imidazolidine and O-ethylS-sec-butyl chlorodithiophosphate are used as starting substances, thesequence of the reaction in process (a) according to the invention canbe outlined by the following equation: ##STR6##

If, for example, 6-chloro-3-chloromethyl-pyridine and O-ethylS-isopropyl 2-cyanoimino-imidazolidine-1-thiophosphonate are used asstarting substances, the sequence of the reaction in process (b)according to the invention can be outlined by the following equation:##STR7##

Formula (II) provides a general definition of the aza compounds to beused as starting substances in process (a) according to the inventionfor the preparation of compounds of the formula (I).

In formula (II), R¹, R², R³ and Y preferably, or in particular, havethose meanings which have already been mentioned in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, or particularly preferred, for R¹, R², R³and Y.

The starting substances of the formula (II) are known and/or can beprepared by processes known per se (cf. EP-A 192,060).

Formula (III) provides a general definition of the chloro-(di)thiophosphoric acid O,S-diesters furthermore to be used as startingsubstances in process (a) according to the invention.

In formula (III), R⁴, R⁵ and X preferably, or in particular, have thosemeanings which have already been mentioned above in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, or particularly preferred, for R⁴, R⁵ andX.

The starting substances of the formula (III) are known and/or can beprepared by processes known per se (cf. DE-A 2,527,308; DE-A 2,615,342;DE-A 2,642,982; DE-A 2,804,796).

Formula (IV) provides a general definition of the heterocyclylmethylchlorides to be used as starting substances in process (b) according tothe invention for the preparation of compounds of the formula (I).

In formula (IV), R¹ preferably, or in particular, has the meaning whichhas already been mentioned above in connection with the description ofthe compounds of the formula (I) according to the invention as beingpreferred, or particularly preferred, for R¹.

The starting substances of the formula (IV) are known and/or can beprepared by processes known per se (cf. J. Heterocycl. Chem. 16 (1979),333-337).

Formula (V) provides a general definition of the phosphorylated azacompounds furthermore to be used as starting substances in process ( b )according to the invention.

In formula (V), R², R³, R⁴, R⁵, X and Y preferably, or in particular,have the meanings which have already been mentioned above in connectionwith the description of the compounds of the formula (I) according tothe invention as being preferred, or particularly preferred, for R², R³,R⁴, R⁵, X and Y.

The starting substances of the formula (V) are known and/or can beprepared by processes known per se (cf. EP-A 277,317).

Processes (a) and (b) according to the invention for the preparation ofthe compounds of the formula (I) are preferably carried out usingdiluents. Diluents which are suitable are virtually all inert organicsolvents. These preferably include aliphatic and aromatic, optionallyhalogenated hydrocarbons, such as pentane, hexane, heptane,cyclohexane,-petroleum ether, benzine, ligroin, benzene, toluene,xylene, methylene chloride, ethylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, ethers, such asdiethyl ether and dibutyl ether, glycol dimethyl ether and diglycoldimethyl ether, tetrahydrofuran and dioxane, ketones, such as acetone,methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone,esters, such as methyl acetate and ethyl acetate, nitriles, such as, forexample, acetonitrile and propionitrile, amides, such as, for example,dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, and alsodimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphorictriamide.

Acid acceptors which can be employed in processes (a) and (b) accordingto the invention are all acid-binding agents which can customarily beused for reactions of this type. The following are preferably suitable:alkali metal hydrides and alkaline earth metal hydrides, such as lithiumhydride, sodium hydride, potassium hydride and calcium hydride, alkalimetal carbonates, alkali metal hydrogen carbonates, alkaline earth metalcarbonates and alkaline earth metal hydrogen carbonates, such as sodiumcarbonate, potassium carbonate, sodium hydrogen carbonate and potassiumhydrogen carbonate and also calcium carbonate, alkali metal acetates,such as sodium acetate and potassium acetate, alkali metal alcoholates,such as sodium tert-butylate and potassium tert-butylate, furthermorebasic nitrogen compounds, such as trimethylamine, triethylamine,tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine,ethyldiisopropylamine, ethyldicyclohexylamine, N,N-dimethylbenzylamine,N,N-dimethyl-aniline, pyridine, 2-methyl-, 3-methyl-, 4-methyl-,2,4-dimethyl-, 2,6-dimethyl-, 2-ethyl-, 4-ethyl- and5-ethyl-2-methyl-pyridine, 1,5-diazabicyclo-[4,3,0]-non-5-ene (DBN),1,8-diazabicyclo[5,4,0]-undec-7-ene (DBU) and1,4-diazabicyclo-[2,2,2]-octane (DABCO).

When carrying out process (a) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between -20° C. and +80° C.preferably at temperatures between 0° C. and 50° C.

When carrying out process (b) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between 0° C. and 120° C.preferably at temperatures between 20° C. and 80° C.

Processes (a) and (b) according to the invention are generally carriedout under atmospheric pressure. However, they can also be carried outunder elevated or reduced pressure.

To carry out processes (a) and (b) according to the invention, thestarting substances required in each case are generally employed inapproximately equimolar amounts. However, it is also possible to use alarger excess of one of the two components employed in each case. Ingeneral, the reactions are carried out in a suitable diluent in thepresence of an acid acceptor, and the reaction mixture is stirred forseveral hours at the temperature required in each case. Working-up iscarried out in each case by customary methods (cf. the PreparationExamples).

The compounds of the general formula (I) are suitable for combatinganimal pests, preferably arthropods and nematodes, in particularinsects, and nematodes in the soil, encountered in agriculture, inforestry, in the protection of stored products and of materials, and inthe hygiene field. They are active against normally sensitive andresistant species and against all or some stages of development. Theabovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber. From the order of theDiplopoda, for example, Blaniulus guttulatus. From the order of theChilopoda, for example, Geophilus carpophagus and Scutigera spec. Fromthe order of the Symphyla, for example, Scutigerella immaculata. Fromthe order of the Thysanura, for example, Lepisma saccharina. From theorder of the Collembola, for example, Onychiurus armatus. From the orderof the Orthoptera, for example, Blatta orientalis, Periplanetaamericana, Leucophaea maderae, Blattella germanica, Acheta domesticus,Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplusdifferentialis and Schistocerca gregaria. From the order of theDermaptera, for example, Forficula auricularia. From the order of theIsoptera, for example, Reticulitermes spp. From the order of theAnoplura, for example, Phylloxera vastatrix, Pemphigus spp., Pediculushumanus corporis, Haematopinus spp. and Linognathus spp. From the orderof the Mallophaga, for example, Trichodectes spp. and Damalinea spp.From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci. From the order of the Heteroptera, for example,Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimexlectularius, Rhodnius prolixus and Triatoma spp. From the order of theHomoptera, for example, Aleurodes brassicae, Bemisia tabaci,Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae,Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum,Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli,Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettixcincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus,Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae,Pseudococcus spp. Psylla spp. From the order of the Lepidoptera, forexample, Pectinophora gossypiella, Bupalus piniarius, Cheimatobiabrumata, Lithocolletis blancardella, Hyponomeuta padella, Plutellamaculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantriaspp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp.,Euxoa spp., Feltia spp., Earias insulana, Hellothis spp., Spodopteraexigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodopteraspp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp.,Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelidesobtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsadecemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodeschrysocephala, Epilachna varive stis, Atomaria spp., Oryzaephilussurinamensis, Antho nomus spp., Sitophilus spp., Otiorrhynchus sulcatus,Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica,Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctusspp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbiumpsylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Cono derusspp., Melolontha melolontha, Amphimallon solsti tialis and Costelytrazealandica. From the order of the Hymenoptera, for example, Diprionspp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp. From the order of the Arachnida, for example, Scorpiomaurus and Latrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp.,Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.

The phytoparasitic nematodes include Pratylenchus spp., Radopholussimilis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heteroderaspp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinemaspp. and Trichodorus spp.

The compounds of the formula (I) according to the invention aredistinguished by an outstanding insecticidal and nematicidal activity.In particular when used against leaf- and soil-dwelling insects whichare harmful to plants, they display a very powerful activity, and alsoagainst nematodes. The excellent (root-systemic) activity againstsoil-dwelling insects and nematodes must be particularly emphasised.

Depending on their particular physical and/or chemical properties, theactive compounds can be converted to the customary formulations, such assolutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols, natural and synthetic materials impregnated with activecompound, very fine capsules in polymeric substances and in coatingcompositions for seed, furthermore formulations used with burningequipment, such as fumigating cartridges, fumigating cans, fumigatingcoils and the like, as well as ULV cold mist and warm mist formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at ambient temperature andunder atmospheric pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide; as solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly disperse silica, alumina and silicates; assolid carriers for granules there are suitable: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust, coconut shells,maize cobs and tobacco stalks; as emulsifying and/or foam-forming agentsthere are suitable: for example non-ionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as well as albumen hydrolysis products; asdispersing agents there are suitable: for example lignin-sulphite wasteliquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The active compounds can be present in their commercially availableformulations and in the use forms, prepared from these formulations, asa mixture with other active compounds, such as insecticides,attractants, sterilising agents, acaricides, nematicides, fungicides,growth-regulating substances or herbicides. The insecticides include,for example, phosphates, carbamates, carboxylates, chlorinatedhydrocarbons, phenylureas and substances produced by microorganisms,inter alia.

The active compounds can furthermore be present in their commerciallyavailable formulations and in the use forms, prepared from theseformulations, as a mixture with synergistic agents. Synergistic agentsare compounds which increase the action of the active compounds, withoutit being necessary for the synergistic agent added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

USE EXAMPLES

In the use examples, the compounds (A) and (B) listed below are used ascomparison compounds: ##STR8##

O-Ethyl S-(1-methylpropyl)(2-oxo-3-thiazolidinyl)phosphonothioate/fosthiazate (disclosed in U.S.Pat. Specification No. 4,509,182). ##STR9##

N-Nitro-1-(6-chloro-3-pyridinyl-methyl)-4,5-dihydro-1H-imidazole-2-amine/imidacloprid(disclosed in EP-A 192,060).

Example A

Critical concentration test/soil insects

Test insect: Diabrotica balteata larvae in the soil

Solvent: 4 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration. The concentration of the activecompound in the preparation is of practically no importance here, onlythe amount by weight of active compound per unit volume of soil, whichis given in ppm (mg/l), being decisive. The soil is transferred into 0.51 pots and the pots are left to stand at 20° C.

Immediately after setting up the experiment, 5 pregerminated maizekernels are placed into each pot. After 1 day, the test insects inquestion are introduced into the treated soil. After a further 7 daysthe degree of effectiveness of the active compound is determined in % bycounting the dead and live test insects. The degree of effectiveness is100% if all the test insects have been killed and is 0% if just as manytest insects are still alive as in the case of the untreated control.

In this test, the compound of Preparation Example 1 showed a degree ofdestruction of 95% at an active compound concentration of 10 ppm, whilethe known active compound (A) showed no effect at the sameconcentration.

Example B

Critical concentration test/root-systemic action

Test insect: Myzus persicae

Solvent: 4 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The preparation of active compound is intimately mixed with soil. Theconcentration of the active compound in the preparation is ofpractically no importance, only the amount by weight of active compoundper unit volume of soil, which is given in ppm (=mg/l), being decisive.The treated soil is transferred into pots and these are planted withcabbage (Brassica oleracea). The active compound can in this way betaken up from the soil by the roots of the plants and be transportedinto the leaves.

To demonstrate the root-systemic effect, the leaves are infested withthe abovementioned test animals after 7 days. After a further 2 days,the evaluation is made by counting or estimating the dead animals. Theroot-systemic action of the active compound is deduced from thedestruction figures. It is 100% if all test animals have been killed and0% if just as many test insects are still alive as in the case of theuntreated control.

In this test, the compounds of Preparation Examples 1 and 2 were fullyactive at an active compound concentration of 2.5 ppm (degree ofdestruction 100%), while the comparison compound (A) showed no effectunder the same conditions.

Example C

Critical concentration test/nematodes

Test nematode: Meloidogyne incognita

Solvent: 4 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The preparation of active compound is intimately mixed with soil whichis severely infested with the test nematode. The concentration of theactive compound in the preparation is of practically no importance, onlythe amount of active compound per unit volume of soil, which is given inppm (=mg/l), being decisive. The treated soil is transferred into pots,lettuce is sown, and the pots are kept at a greenhouse temperature of25° C.

After four weeks, the lettuce roots are examined for nematodeinfestation (root galls), and the degree of effectiveness is 100% ifinfestation is avoided completely and 0% if the level of infestation isjust as high as in the control plants in untreated, but equallyinfested, soil.

In this test, the compound of Preparation Example 1 showed a degree ofdestruction of 100% at an active compound concentration of 20 ppm.

Under these conditions, comparison compound (B) exhibited no activityagainst the test nematode Meloidogyne incognita.

Example D

Critical concentration test/nematodes

Test nematode: Globodera rostochiensis

Solvent: 4 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The preparation of active compound is intimately mixed with soil whichis severely infested with the test nematode. The concentration of theactive compound in the preparation is of practically no importance, onlythe amount of active compound per unit volume of soil, which is given inppm (=mg/l), being decisive. The treated soil is transferred into pots,potatoes are planted, and the pots are kept at a greenhouse temperatureof 20° C.

After 6 weeks, the potato roots are examined for cysts, and the degreeof effectiveness of the active compound is determined in %. The degreeof effectiveness is 100% if infestation is avoided completely and 0% ifthe level of infestation is just as high as in the control plants inuntreated, but equally infested, soil.

In this test, the compound of Preparation Example 1 showed a degree ofdestruction of 100% at an active compound concentration of 20 ppm.

Under these conditions, comparison compound (B) exhibited no activityagainst the test nematode Globodera rostochiensis.

Example E

Seed treatment test/soil insects

Test insect: Diabrotica balteata larvae in the soil

Test plant: Zea mays

Solvent: 1 part by weight of acetone

Excipient: kaolin

To produce a suitable preparation of active compound, the activecompound is dissolved in acetone and 1 part by weight of activecompound/acetone is mixed with 5 parts by weight of kaolin. The maizeseed is treated with this active compound preparation at the applicationrates required. It is sown in 0.5 1 pots containing standardised soilsat a greenhouse temperature of 20° C.

After 1 day, approx. 30 Diabrotica larvae are placed into each pot.After a further 7 days, the degree of action is determined in % bycounting the dead and live test insects. The degree of action of 100%when all test insects have been destroyed, it is 0% when just as manytest insects are alive as in the untreated control.

In this test, the compound of Preparation Example 1 caused a degree ofdestruction of 100% at an active compound concentration of 0.5 g/kg ofseed, while compound (A) showed no effect under the same conditions.

Example F

Seed treatment test/root-systemic action

Test insect: Aphis fabae

Test plant: Vicia faba

Solvent: 1 part by weight of acetone

Excipient: kaolin

To produce a suitable preparation of active compound, the activecompound is dissolved in acetone and 1 part by weight of activecompound/acetone is mixed with 5 parts by weight of kaolin. The beanseed is treated with this preparation of active compound at theapplication rates required. The field beans are sown in 0.5 1 potscontaining standardised soils at room temperatures of 20° C.

The active compound can thus be taken up from the soil by the plantroots and transported into the leaves.

For detection of the root-systemic effect, the leaves only are infestedwith the abovementioned test animals after 14 days. After a further 3days, the evaluation is carried out by counting or estimating the deadanimals. The root-systemic action of the active compound is derived fromthe destruction figures. It is 100% if all the test animals have beenkilled and 0% if just as many test insects are still alive as in theuntreated control.

In this test, the compound of Preparation Example 1 caused a degree ofdestruction of 100% at an active compound concentration of 0.25 g/kg ofseed, while compound (A) showed no effect under the same conditions.

Example G

Phaedon larvae test

Solvent: 7 parts by weight of dimethyl formamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of the active compound of the desired concentration and areinfested with mustard beetle larvae (Phaedon cochleariae) while theleaves are still moist.

After the specified periods of time, the destruction in % is determined.100% means that all the beetle larvae have been killed; 0% means thatnone of the beetle larvae have been killed.

In this test, a superior activity compared with the comparison compound(A) is shown, for example, by the following compounds of the preparationexamples: 1 and 2.

PREPARATION EXAMPLES Example 1 ##STR10##

6.7 g (0.06 mol) of potassium tert-butanolate are added at 25°-30° C. toa mixture of 12.7 g (0.05 mol) of1-(6-chloro-3-pyridinylmethyl)-2-nitroimino-imidazolidine and 80 ml oftetrahydrofuran. This solution is treated, at 5° C., with 10.9 g (0.05mol) of S-sec-butyl O-ethyl chlorothiophosphate, and stirring iscontinued overnight at room temperature. The solvent is then removed bydistillation in vacuo, and 100 ml of ethyl acetate and 100 ml of waterare added. The mixture is shaken; the organic phase is then separatedoff. It is dried over sodium sulphate and evaporated in vacuo. Remainingvolatile components are stripped from the residue at 60° C. under anoil-pump vacuum.

16.7 g (77% of theory) of O-ethyl S-sec-butyl 3-(6-chloro-3-pyridinylmethyl)-2-nitroimino-imidazolidine-1-thiophosphonate are obtained as ayellow oil of refractive index [α]_(D) ²³ =1.5655.

Example 2

O-Ethyl S-sec-butyl3-(6-chloro-3-pyridinyl-methyl)-2-nitroimino-imidazolidine-1-dithiophosphonateof refractive index [α]_(D) ²³ =1.5960 ##STR11## is also obtainedanalogously to Example 1.

Other compounds of the formula (I) ##STR12## which can be preparedanalogously to Examples 1 and 2 are the following:

                                      TABLE                                       __________________________________________________________________________                                        Physi-                                                                        cal                                       Ex.                                 con-                                      No.                                                                              R.sup.1  R.sup.2                                                                           R.sup.3                                                                            R.sup.4                                                                          R.sup.5                                                                              X Y  stants                                    __________________________________________________________________________     3                                                                                ##STR13##                                                                             CH.sub.2CH.sub.2                                                                       C.sub.2 H.sub.5                                                                   ##STR14##                                                                           O NO.sub.2                                      4                                                                                ##STR15##                                                                             CH.sub.2CH.sub.2                                                                       C.sub.2 H.sub.5                                                                   ##STR16##                                                                           S NO.sub.2                                      5                                                                                ##STR17##                                                                             (CH.sub.2).sub.3                                                                       C.sub.2 H.sub.5                                                                   ##STR18##                                                                           O NO.sub.2                                      6                                                                                ##STR19##                                                                             (CH.sub.2).sub. 3                                                                      C.sub.2 H.sub.5                                                                   ##STR20##                                                                           S NO.sub.2                                      7                                                                                ##STR21##                                                                             H   CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   ##STR22##                                                                           O NO.sub.2                                      8                                                                                ##STR23##                                                                             CH.sub.3                                                                          H    C.sub.2 H.sub.5                                                                   ##STR24##                                                                           O NO.sub.2                                      9                                                                                ##STR25##                                                                             CH.sub.3                                                                          CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   ##STR26##                                                                           O NO.sub.2                                     10                                                                                ##STR27##                                                                             CH.sub.3                                                                          CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   ##STR28##                                                                           S NO.sub.2                                     11                                                                                ##STR29##                                                                             CH.sub.2CH.sub.2                                                                       C.sub.2 H.sub.5                                                                   ##STR30##                                                                           O NO.sub.2                                     12                                                                                ##STR31##                                                                             CH.sub.2CH.sub.2                                                                       C.sub.2 H.sub.5                                                                   ##STR32##                                                                           S NO.sub.2                                     13                                                                                ##STR33##                                                                             (CH.sub.2).sub.3                                                                       C.sub.2 H.sub.5                                                                   ##STR34##                                                                           O NO.sub.2                                     14                                                                                ##STR35##                                                                             (CH.sub.2).sub.3                                                                       C.sub.2 H.sub.5                                                                   ##STR36##                                                                           S NO.sub.2                                     15                                                                                ##STR37##                                                                             CH.sub.2CH.sub.2                                                                       C.sub.3 H.sub.7                                                                   ##STR38##                                                                           O NO.sub.2                                     16                                                                                ##STR39##                                                                             CH.sub.2CH.sub.2                                                                       C.sub.2 H.sub.5                                                                  CH(CH.sub.3).sub.2                                                                   O NO.sub.2                                     __________________________________________________________________________

We claim:
 1. Phosphorylated aza compounds of the formula (I) ##STR40##in which R¹ represents a five- or six-membered heterocyclic groupselected from the group consisting of furyl, thienyl, pyrrolyl,pyrazolyl, imidazolyl, 1,2,3- or 1,2,4-triazolyl, oxazolyl, isoxazolyl,1,2,4- or 1,3,4-oxadiazolyl, thiazolyl, isothiazolyl, 1,2,3-, 1,2,4-,1,2,5- or 1,3,4-thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl andpyrazinyl, each of which is optionally substituted by fluorine,chlorine, bromine, iodine, cyano, nitro, C₁ -C₄ -alkyl (which isoptionally substituted by fluorine and/or chlorine), C₂ -C₄ -alkenyl(which is optionally substituted by fluorine and/or chlorine), C₂ -C₄-alkinyl, C₁ -C₄ -alkoxy (which is optionally substituted by fluorineand/or chlorine), C₃ -C₄ -alkenyloxy (which is optionally substituted byfluorine and/or chlorine), C₃ -C₄ -alkinyloxy, C₁ -C₄ -alkylthio (whichis optionally substituted by fluorine and/or chlorine), C₃ -C₄-alkenylthio (which is optionally substituted by fluorine and/orchlorine), C₃ -C₄ -alkinylthio, C₁ -C₄ -alkylsulphinyl (which isoptionally substituted by fluorine and/or chlorine), C₁ -C₄-alkylsulphonyl (which is optionally substituted by fluorine and/orchlorine), amino, C₁ -C₄ -alkylamino, di-(C₁ -C₄ -alkyl)-amino, phenyl,phenoxy, phenylthio, phenylamino, benzyl, formylamino, C₁ -C₄-alkylcarbonylamino, formyl, carbamoyl, C₁ -C₄ -alkylcarbonyl and/or C₁-C₄ -alkoxy-carbonyl,R² represents hydrogen or C₁ -C₃ -alkyl, R³represents hydrogen or C₁ -C₃ -alkyl or together with R² represents C₂-C₄ -alkanediyl, R⁴ represents C₁ -C₄ -alkyl, R⁵ represents C₁ -C₅-alkyl, X represents oxygen or sulphur and Y represents nitro orcyano,with the exception of the compound O-ethyl S-propyl3-(6-chloro-3-pyridinylmethyl)-2-nitroimino-imidazolidine-1-thiophosphonate.2. Compounds of the formula (I) according to claim 1 wherein in thatR¹represents a five- or six-membered heterocyclic group selected from thegroup consisting of pyrazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl,thiazolyl, isothiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrazinyl andpyrimidinyl, each of which is optionally substituted by fluorine,chlorine, bromine, cyano, nitro, C₁ -C₂ -alkyl (which is optionallysubstituted by fluorine and/or chlorine), C₁ -C₂ -alkoxy (which isoptionally substituted by fluorine and/or chlorine), C₁ -C₂ -alkylthio(which is optionally substituted by fluorine and/or chlorine) or C₁ -C₂-alkyl sulphonyl (which is optionally substituted by fluorine and/orchlorine), R² represents hydrogen or methyl, R³ represents hydrogen ormethyl or together with R² represents dimethylene or trimethylene, R⁴represents ethyl, propyl or isopropyl, R⁵ represents ethyl, propyl,isopropyl, butyl, isobutyl or sec-butyl, X represents oxygen or sulphurand Y represents nitro or cyano,with the exception of the compoundO-ethyl S-propyl3-(6-chloro-3-pyridinylmethyl)-2-nitroimino-imidazolidine-1-thiophosphonate.3. Compounds of the formula (I) according to claim 1 wherein in thatR¹represents 6-chloro-3-pyridinyl or 2-chloro-5-thiazolyl, R² and R³together represent dimethylene (--CH₂ CH₂ --) or trimethylene (--CH₂ CH₂CH₂ --) R⁴ represents ethyl, R⁵ represents sec-butyl, X representsoxygen or sulphur and Y represents nitro.
 4. A pesticidal compositioncomprising a pesticidally effective amount of at least onephosphorylated aza compound of the formula (I) according to claim 1 andan extender.
 5. A method of combating animal pests comprising applyingto said animal pests or their habitat a pesticidally effective amount ofat least one phosphorylated aza compound of the formula (I) according toclaim
 1. 6. The method according to claim 5, wherein said animal pestsare soil-dwelling nematodes.
 7. The method according to claim 5, whereinsaid animal pests are soil-dwelling insects.